JP6002383B2 - Oil composition - Google Patents

Description

  The present invention relates to an oil / fat composition containing a plant sterol in a dissolved state.

Plant sterols are steroid alcohols that are widely present in plants in the free state or in the form of fatty acid esters, glycosides, ferulic acid esters and the like. Since plant sterol has an excellent blood cholesterol lowering effect, it has been blended into edible fats and oils. Among plant sterols, β-sitosterol is considered to have an excellent cholesterol-lowering effect (Non-patent Documents 1 and 2).
However, plant sterols are hydrolyzed at the stage of extraction, concentration and purification from natural products, and are almost free. However, this free state of plant sterols dissolves very little in edible fats and oils. There is.

  Therefore, techniques for solubilizing plant sterols in edible fats and oils have been studied. For example, a method of solubilizing plant sterols in oil using a large amount of vitamin E and an emulsifier (Patent Document 1), plant sterols in the form of fatty acid esters A method of adding to oils and fats (Patent Document 2) has been proposed. In addition, in edible oils and fats containing oryzanol and triterpene alcohol having physiological effects similar to those of plant sterols together with plant sterols, when the content of free type of triterpene alcohol and plant sterols is below a certain amount, it is excellent as edible oils and fats (Patent Document 3)

Japanese Patent Laid-Open No. 10-179086 Japanese Patent Laid-Open No. 11-127779 JP 2001-224309 A

Atherosclerosis, 28, 325-338 (1977) The lipid vol. 5, no. 1,101-105 (1994)

  Edible fats and oils containing conventional plant sterols have a clear appearance at the time of preparation, but during storage, there is a problem that crystals of plant sterols are produced when stored under low temperature or high temperature and high humidity conditions. . Insolubilized plant sterols are difficult to be absorbed in the body, and it is difficult to effectively exert a blood cholesterol lowering effect.

  Accordingly, an object of the present invention is to provide an oil and fat composition in which plant sterol is dissolved at a high concentration and crystallization is suppressed even during storage under low temperature or high temperature and high humidity conditions.

  As a result of intensive studies to solve the above problems, the present inventors have demonstrated that free triterpene alcohol exhibits an excellent crystal suppression effect on plant sterols, and the free triterpene alcohol coexists in a certain range in fats and oils. As a result, it was found that an oil and fat composition in which free plant sterols, particularly β-sitosterol was dissolved at a high concentration was obtained.

That is, the present invention includes the following components (A) and (B):
(A) Free triterpene alcohol 0.4-6 mass%,
(B) 0.2 to 3% by mass of free plant sterol containing 20% by mass or more of β-sitosterol,
And (A) a free triterpene alcohol and (B) a free plant sterol containing mass ratio [(A) / (B)] of 0.9 or more is provided.

  According to the present invention, it is possible to provide an oil or fat composition having a high content of plant sterols, particularly β-sitosterol, having excellent physiological effects, and having suppressed crystallization at low temperatures and the like.

In this specification, the triterpene alcohol is a tetracyclic triterpene alcohol having 30 or 31 carbon atoms.
Triterpene alcohol can be obtained by extraction from fats and oils containing processed triterpene alcohol such as rice, rice bran, and rice oil, and hydrolysis of γ-oryzanol. Moreover, a commercial item can be used.

Moreover, in this specification, plant sterol is C28 or 29-desmethyl sterol. The plant sterol and the triterpene alcohol are clearly different compounds.
Plant sterols can be obtained by extraction from plants such as vegetables, beans, and grains, hydrolysis of γ-oryzanol, and known organic chemical synthesis methods. Moreover, a commercial item can be used.

  Triterpene alcohols and plant sterols include free, fatty acid ester, and ferulic acid ester types. In this specification, the free type refers to those having a hydroxyl group at the C-3 position of the steroid nucleus.

Examples of the free triterpene alcohol (A) used in the present invention include cycloartenol, 24-methylenecycloartanol, cyclobranol, cycloartanol, cyclosador, cyclolaudenol, butyrosperimol, parqueol, and the like. Is mentioned. The free triterpene alcohol can be used as a single compound or as a mixture. Among these, from the viewpoint of physiological effects, one or more selected from cycloartenol, 24-methylenecycloartanol and cyclobranol are preferable, and cycloartenol, 24-methylenecycloartanol or these It is more preferable to use a combination.
Free triterpene alcohols are described in J. Org. Am. Oil Chem. Soc. , 82 (6), 439 (2005).

The oil and fat composition of the present invention contains (A) 0.4 to 6% by mass (hereinafter simply referred to as “%”) of free triterpene alcohol. By making the content of component (A) within such a certain range, the solubility of free plant sterols in fats and oils can be increased, and crystallization of free plant sterols is suppressed during storage, especially even at low temperature storage can do. That is, (A) free triterpene alcohol can be used to improve the solubility of fat-type plant sterols containing β-sitosterol in an amount of 20% or more in fats and oils, and the free triterpene alcohol is free under normal temperature, low temperature or high temperature and high humidity conditions Can be used to suppress crystallization of type plant sterols. Moreover, (A) free type | mold triterpene alcohol can be used for the stability improvement in normal temperature, low temperature, or high temperature / humidity conditions of the fats and oils which contain the said free type | mold plant sterol 0.2 to 3%.
The content of (A) free triterpene alcohol in the oil and fat composition is 0.85% or more, further 0.9% or more, further 1.2% or more, further 1.6% or more, and further 2.1%. The above is preferable from the viewpoint of physiological effects, and is 6% or less, further 5% or less, further 0.4 to 5%, and further 0.4 to 4% is a point to improve the cold resistance. From the viewpoint of improving the stability under high temperature and high humidity conditions.

  In addition, in the free triterpene alcohol (A), the content of cycloartenol is preferably 15 to 100%, more preferably 20 to 90%, and further preferably 25 to 80% from the viewpoint of physiological effects.

  The oil and fat composition of the present invention contains (B) 0.2 to 3% of a free plant sterol, but further contains 0.2 to 2.5%, and more preferably 0.2 to 2%. From the viewpoint of improving the properties.

  (B) Free type plant sterol used by this invention contains (beta) -sitosterol 20% or more. The content of β-sitosterol in the free plant sterol is further 20 to 100%, further 20 to 90%, further 20 to 80%, further 20 to 70%, further 20 to 60%, and further 20 to 40%. It is preferable from the viewpoint of improving the cold resistance.

(B) The free plant sterol preferably contains campesterol in addition to β-sitosterol from the viewpoint of suppression of crystallization.
(B) The content of campesterol in the free-type plant sterol is 5 to 80%, further 10 to 80%, further 20 to 75%, and further 30 to 70%, which is stable under high temperature and high humidity conditions. From the viewpoint of improving the properties.

(B) The free plant sterols include plant sterols other than β-sitosterol and campesterol, such as α-sitosterol, stigmasterol, α-sitostanol, β-sitostanol, stigmasteranol, campestanol, and brassicasterol. , 1 type (s) or 2 or more types selected from fucosterol, isofucostol, spinasterol, abenasterol and the like may be contained.
Free plant sterols are described in J. Org. Am. Oil Chem. Soc. , 82 (6), 439 (2005).

  In the oil and fat composition of the present invention, the content mass ratio [(A) / (B)] of (A) free triterpene alcohol and (B) free plant sterol is 0.9 or more, and more preferably 0.9 to 6. Further 0.9 to 5, further 0.9 to 4, further 0.9 to 3.5, 0.9 to 3 increase the solubility of free plant sterols, and crystals of the plant sterols This is preferable from the viewpoint of suppressing the conversion.

In the oil and fat composition of the present invention, the content of the fatty acid ester type triterpene alcohol is less than 1.4%, further less than 0.5%, further less than 0.1%, further less than 0.05%, and further 0.01%. Less than, further 0-1.4%, further 0.0001-0.5%, further 0.0001-0.08%, and further 0.0001-0.04% is a point that improves the flavor. To preferred. Fatty acid ester type triterpene alcohol is disclosed in J. Org. It can be measured according to the method described in Food Science, 65 (8), 1395 (2000).
The fatty acid ester type triterpene alcohol can be calculated from the total triterpene alcohol amount, the free triterpene alcohol amount, and the ferulic acid ester type triterpene alcohol amount. The total amount of triterpene alcohol is J.A. Am. Oil Chem. Soc. , 82 (6), 439 (2005), and ferulic acid ester type triterpene alcohol is disclosed in J. Am. It can be measured according to the method described in Food Science, 65 (8), 1395 (2000) and Lipids, 30 (3), 269 (1995).
The fatty acid ester type triterpene alcohol refers to a triterpene alcohol in which a fatty acid is ester-bonded to the hydroxyl group at the C-3 position of the free triterpene alcohol.

In the oil and fat composition of the present invention, the content of γ-oryzanol is less than 0.7%, further less than 0.5%, further less than 0.15%, further less than 0.1%, and further 0.05%. Less than 0.01%, further less than 0.0034%, further less than 0.001%, further less than 0.0002%, further 0 to 0.5%, further 0.000001 to 0.1%, further 0 It is preferably 0.000001 to 0.01%, more preferably 0.000001 to 0.003%, and still more preferably 0.000001 to 0.0001% from the viewpoint of improving the flavor.
Here, γ-oryzanol is a substance present in rice oil, corn oil, and other cereal bran oils, and is a general term for the above-mentioned triterpene alcohol and sterol ferulic acid (3-methoxy-4-hydroxycinnamic acid) ester. . γ-Oryzanol is described in J. Org. It can be measured according to the method described in Food Science, 65 (8), 1395 (2000) and Lipids, 30 (3), 269 (1995).

  There is no particular limitation on fats and oils (edible fats and oils) that can be used in the oil and fat composition of the present invention, such as soybean oil, rapeseed oil, safflower oil, rice oil, corn oil, palm oil, sunflower oil, cottonseed oil, olive oil, sesame oil, Peanut oil, pearl barley oil, wheat germ oil, perilla oil, flaxseed oil, sesame oil, sacha inch oil, walnut oil, kiwi seed oil, salvia seed oil, grape seed oil, macadamia nut oil, hazelnut oil, pumpkin seed oil, straw oil, tea Vegetable oil such as real oil, borage oil, palm oil, palm olein, palm stearin, palm oil, palm kernel oil, cocoa butter, monkey fat, shea fat, algae oil; fish oil, lard, beef fat, butter fat, etc. Animal fats and oils; or fats and oils such as transesterified oils, hydrogenated oils, and fractionated oils. These oils may be used alone or in combination as appropriate. Especially, it is preferable to use vegetable oil and fat from the point of usability, and it is preferable to use liquid oil and fat excellent in low temperature tolerance. “Liquid fats and oils” refers to fats and oils that are liquid at 20 ° C. when a cooling test according to the standard fat analysis method 2.3.8-27 is performed. Moreover, it is preferable that edible fats and oils are the refined fats and oils which passed through the refinement | purification process.

In the oil and fat composition of the present invention, the content of oil and fat is preferably 90 to 99.4%, more preferably 94 to 99%, and further preferably 97 to 99% from the viewpoint of use.
The oil and fat of the present invention contains one or more of monoacylglycerol, diacylglycerol, and triacylglycerol, but the content of diacylglycerol in the oil and fat composition is preferably 19% or less, and more preferably 9% or less. Further, 0.1 to 7% and further 0.2 to 5% are preferable from the viewpoint of industrial productivity of fats and oils. Further, the content of monoacylglycerol is preferably 3% or less, more preferably 0 to 2% from the viewpoint of improving the flavor. The content of triacylglycerol is preferably 78 to 99.4%, more preferably 88 to 99.4%, further 90 to 99.4%, and further 92 to 99% from the viewpoint of industrial productivity of fats and oils. preferable.

  Further, the content of free fatty acid or salt thereof contained in the oil and fat composition of the present invention is preferably 5% or less, more preferably 0 to 2%, and more preferably 0 to 1%. This is preferable.

  Fatty acids constituting the fats and oils in the fat and oil composition of the present invention are not particularly limited and may be either saturated fatty acids or unsaturated fatty acids, but 60 to 100% are preferably unsaturated fatty acids, more It is preferably 70 to 100%, more preferably 75 to 100%, and further preferably 80 to 98% in terms of appearance and industrial productivity of fats and oils. The number of carbon atoms of the unsaturated fatty acid is preferably 14 to 24, and more preferably 16 to 22 from the viewpoint of physiological effects.

  Moreover, it is preferable that content of saturated fatty acid is 40% or less among the fatty acids which comprise the fats and oils in fats and oils composition, More preferably, it is 0 to 30%, Furthermore, 0 to 25%, Furthermore, it is 2 to 20%. It is preferable in terms of appearance, physiological effect, and industrial productivity of fats and oils. Saturated fatty acids are preferably those having 14 to 24 carbon atoms, and more preferably 16 to 22 carbon atoms.

  Furthermore, the oil and fat composition of the present invention preferably contains 0.01 to 2% of an antioxidant in the oil and fat composition from the viewpoint of oxidation stability during storage and cooking, and more preferably 0.01 to 1 %, More preferably 0.01 to 0.5%. The antioxidant is preferably one or more selected from natural antioxidants, tocopherols, ascorbyl palmitate, ascorbyl stearate, dibutylhydroxytoluene (BHT) and butylhydroxyanisole (BHA), and more preferable examples. As one or more antioxidants selected from natural antioxidants, tocopherols and ascorbyl palmitate. Among these, the combined use of ascorbyl palmitate and tocopherol is preferable.

  The oil and fat composition of the present invention can be used in the same manner as general edible oils and fats and can be widely applied to various foods and drinks using oils and fats.

In relation to the above-described embodiment, the present invention discloses the following oil composition or use.
<1> The following components (A) and (B):
(A) Free triterpene alcohol 0.4-6%,
(B) 0.2 to 3% of free plant sterol containing 20% or more of β-sitosterol, and (A) the content mass ratio of free triterpene alcohol and (B) free plant sterol [(A ) / (B)] is 0.9 or more.
<2> The content of (A) free triterpene alcohol is preferably 0.85% or more, more preferably 0.9% or more, further preferably 1.2% or more, more preferably 1.6% or more, More preferably, it is 2.1% or more, The oil-fat composition as described in said <1>.
<3> The fat and oil composition according to <1> or <2>, wherein the content of (A) free triterpene alcohol is preferably 6% or less, more preferably 5% or less.
<4> The fat and oil composition according to <1>, wherein the content of (A) free triterpene alcohol is preferably 0.4 to 5%, more preferably 0.4 to 4%.

<5> (A) The free triterpene alcohol is selected from cycloartenol, 24-methylenecycloartanol, cyclobranol, cycloartanol, cyclosador, cyclolaudenol, butyrosperimol and parqueol, or Two or more, preferably one or more selected from cycloartenol, 24-methylenecycloartanol and cyclobranol, more preferably cycloartenol, 24-methylenecycloartanol or these Oil composition according to <1> to <4>, which is a combination.

<6> (B) The content of the free plant sterol is preferably 0.2 to 2.5%, more preferably 0.2 to 2%, according to 1 of <1> to <5> above. Oil composition.
<7> (B) The content of β-sitosterol in the free plant sterol is preferably 20 to 100%, more preferably 20 to 90%, still more preferably 20 to 80%, and still more preferably 20 to 70%. More preferably, it is 20-60%, More preferably, it is 20-40%, The oil-fat composition of 1 of said <1>-<6>.
<8> (B) The fat composition according to <1> to <7>, wherein the free plant sterol contains campesterol in addition to β-sitosterol.
<9> (B) The content of campesterol in the free plant sterol is 5 to 80%, preferably 10 to 80%, more preferably 20 to 75%, and further preferably 30 to 70%. <8> The oil and fat composition as described.
<10> The mass ratio [(A) / (B)] of (A) free triterpene alcohol and (B) free plant sterol is preferably 0.9 to 6, more preferably 0.9 to 5. More preferably, it is 0.9-4, More preferably, it is 0.9-3.5, More preferably, it is 0.9-3, Oil-fat composition of 1 of said <1>-<9>.
<11> The fat composition according to <1> to <10>, wherein the content of the fat is 90 to 99.4%, preferably 94 to 99%, and more preferably 97 to 99%.

<12> The content of triacylglycerol is 78 to 99.4%, preferably 88 to 99.4%, more preferably 90 to 99.4%, and still more preferably 92 to 99%. The oil-and-fat composition as described in 1 of>-<11>.
<13> 60 to 100%, preferably 70 to 100%, more preferably 75 to 100%, and still more preferably 80 to 98% of the fatty acids constituting the fats and oils in the fat and oil composition, Oil composition according to 1 of <1> to <12>.
<14> 40% or less, preferably 0 to 30%, more preferably 0 to 25%, and still more preferably 2 to 20% of the fatty acid constituting the oil or fat in the oil or fat composition, the above <1>. ~ Oil composition according to 1 of <13>.

<15> The content of the fatty acid ester type triterpene alcohol is less than 1.4%, preferably less than 0.5%, more preferably less than 0.1%, still more preferably less than 0.05%, and still more preferably 0.8. The fat composition according to <1> to <14>, which is less than 01%.
<16> Fatty acid ester type triterpene alcohol content is 0 to 1.4%, preferably 0.0001 to 0.5%, more preferably 0.0001 to 0.08%, and still more preferably 0.0001 to Oil composition according to <1> to <14>, which is 0.04%.
<17> The content of γ-oryzanol is less than 0.7%, preferably less than 0.5%, more preferably less than 0.15%, further preferably less than 0.1%, more preferably 0.05%. <1> to <16>, more preferably less than 0.01%, more preferably less than 0.0034%, still more preferably less than 0.001%, and still more preferably less than 0.0002%. The oil-and-fat composition described in 1.
The content of <18> γ-oryzanol is 0 to 0.5%, preferably 0.000001 to 0.1%, more preferably 0.000001 to 0.01%, and still more preferably 0.000001 to 0.00. The oil and fat composition according to <1> to <16>, which is 003%, more preferably 0.000001 to 0.0001%.
<19> Further containing an antioxidant in an amount of 0.01 to 2%, preferably 0.01 to 1%, more preferably 0.01 to 0.5%. The oil-and-fat composition as described.
<20> Antioxidant is one or more selected from natural antioxidants, tocopherol, ascorbyl palmitate, ascorbyl stearate, dibutylhydroxytoluene and butylhydroxyanisole, preferably tocopherol, ascorbyl palmitate and The fat and oil composition according to <19>, which is one or more selected from ascorbyl stearate, and more preferably a combination of tocopherol and ascorbyl palmitate.

<21> Use of the oil and fat composition according to <1> to <20> as an edible oil or fat.
<22> Use of a free triterpene alcohol for improving the solubility of a free plant sterol containing 20% or more of β-sitosterol in fats and oils.
Use of free triterpene alcohol for suppressing crystallization of fat-free plant sterols containing <23> β-sitosterol in a fat or oil under normal temperature, low temperature or high temperature and high humidity conditions.
<24> Use of a free triterpene alcohol for improving the stability of a fat or oil containing 0.2 to 3% of a free plant sterol containing 20% or more of β-sitosterol under normal temperature, low temperature or high temperature and high humidity conditions.
<25> The content of β-sitosterol in the free plant sterol is preferably 20 to 100%, more preferably 20 to 90%, still more preferably 20 to 80%, still more preferably 20 to 70%, and still more preferably. Is 20 to 60%, more preferably 20 to 40%, according to <1> of <22> to <24> above.
<26> The use according to 1 of <22> to <25>, wherein the free plant sterol contains campesterol in addition to β-sitosterol.
<27> The content of campesterol in the free plant sterol is 5 to 80%, preferably 10 to 80%, more preferably 20 to 75%, and further preferably 30 to 75%, <26> Use as described in.
<28> One or more free triterpene alcohols selected from cycloartenol, 24-methylenecycloartanol, cyclobranol, cycloartanol, cyclosador, cyclolaudenol, butyrosperimol and parqueol Preferably, it is one or more selected from cycloartenol, 24-methylenecycloartanol and cyclobranol, more preferably cycloartenol, 24-methylenecycloartanol or a combination thereof. The use according to 1 of <22> to <27>.
<29> The content of the free plant sterol in the fat is preferably 0.2 to 2.5%, more preferably 0.2 to 2%, according to 1 of <22> to <29> above Use of.
<30> The content of free triterpene alcohol is 0.4% or more, preferably 0.85% or more, more preferably 0.9% or more, still more preferably 1.2% or more, and still more preferably 1.6. % Or more, More preferably, the use according to 1 of <22> to <29> above, wherein free triterpene alcohol is contained in an oil or fat so as to be 2.1% or more.
<31> The <22> to <30>, wherein the free triterpene alcohol is contained in an oil or fat so that the content of the free triterpene alcohol is 6% or less, preferably 5% or less. Use of.
<32> Free triterpene alcohol is contained in fats and oils so that the content of free triterpene alcohol is 0.4 to 6%, preferably 0.4 to 5%, more preferably 0.4 to 4% or less. The use <33> of <22> to <29>, wherein the content mass ratio [(A) / (B)] of the free triterpene alcohol and the free plant sterol is 0.9 or more, Preferably 0.9 to 6, more preferably 0.9 to 5, more preferably 0.9 to 4, more preferably 0.9 to 3.5, more preferably 0.9 to 3, The use according to <1> of <22> to <32>, wherein the oil or fat contains free triterpene alcohol and free plant sterol.

[Analysis method]
(I) Fatty acid glyceride composition About 10 mg of an oil and fat sample and 0.5 mL of a trimethylsilylating agent (“silylating agent TH”, manufactured by Kanto Chemical) were added to a glass sample bottle, sealed, and heated at 70 ° C. for 15 minutes. To this, 1.0 mL of water and 1.5 mL of hexane were added and shaken. After standing, the upper layer was analyzed by gas chromatography (GLC).
<GLC analysis conditions>
(conditions)
Equipment: Agilent 6890 series (manufactured by Agilent Technologies)
Integrator: ChemStation B 02.01 SR2 (manufactured by Agilent Technologies)
Column: DB-1ht (manufactured by Agilent J & W)
Carrier gas: 1.0 mL He / min
Injector: Split (1:50), T = 340 ° C.
Detector: FID, T = 350 ° C
Oven temperature: Increased from 80 ° C to 340 ° C at 10 ° C / min and held for 15 minutes

(ii) Constituent Fatty Acid Composition of Fats and Oils Fatty acid methyl esters were prepared according to “Preparation Method of Fatty Acid Methyl Esters (2.4.1.-1996)” in “Standard Fat and Fat Analysis Test Method” edited by Japan Oil Chemists' Society. Oil samples were obtained from American Oil Chemists. It was measured by Society Official Method Ce 1f-96 (GLC method).
<GLC analysis conditions>
Column: CP-SIL88 100 m × 0.25 mm × 0.2 μm (Varian)
Carrier gas: 1.0 mL He / min
Injector: Split (1: 200), T = 250 ° C.
Detector: FID, T = 250 ° C
Oven temperature: Hold at 174 ° C for 50 minutes, then heat up to 220 ° C at 5 ° C / minute and hold for 25 minutes

(Iii) Free Triterpene Alcohol and Free Plant Sterol Am. Oil Chem. Soc. 82 (6), 439 (2005), samples were prepared and subjected to GLC for analysis. Specifically, it measured by the following method.
About 500 mg of an oil and fat sample was dissolved in about 5 mL of hexane, and charged into an SPE cartridge (Sep-Pak Silica, 5 g, GL Science). After washing with about 40 mL of hexane / ether (volume ratio 95/5), elution was performed with about 40 mL of ethanol / ether / hexane (volume ratio 50/25/25), and the ethanol / ether / hexane elution fraction was fractionated. The solvent was distilled off from the obtained fraction and charged to PTLC (Si60, 20 × 20 × 0.1 cm, Merck). After developing sequentially with hexane / ether / acetic acid (volume ratio 90/10/2) and chloroform / ether (volume ratio 95/5), a free triterpene alcohol part and a free plant sterol part were separated. The separated free triterpene alcohol fraction or free plant sterol fraction and 0.5 mL of a trimethylsilylating agent (“silylating agent TH”, manufactured by Kanto Chemical) were added, sealed, and heated at 70 ° C. for 30 minutes. . To this, 1.0 mL of water and 1.5 mL of hexane were added and shaken. After standing, the upper layer was subjected to gas chromatography (GLC) and analyzed, and the amount of free triterpene alcohol and the amount of free plant sterol (% by mass) were measured.
<GLC analysis conditions>
Column: DB-1ht 10.0 m × 0.25 mm × 0.10 μm (Agilent)
Carrier gas: 1.0 mL He / min
Injector: Split (1:80), T = 340 ° C.
Detector: FID, T = 350 ° C
Oven temperature: raised from 200 ° C to 340 ° C at 10 ° C / min and held for 10 minutes

(Iv) Total triterpene alcohol Am. Oil Chem. Soc. , 82 (6) 439 (2005), samples were prepared and measured by GLC. Specifically, it measured by the following method.
To an Erlenmeyer flask, about 5 g of an oil and fat sample and about 20 mL of a 2N potassium hydroxide / ethanol solution were added and heated at 80 ° C. for 60 minutes. After cooling to room temperature, an internal standard (cholesterol), 15 mL of water, and 10 mL of hexane were added and shaken. After standing, the upper layer was separated and concentrated. To the concentrate, 0.5 mL of a trimethylsilylating agent (“silylating agent TH”, manufactured by Kanto Chemical Co., Inc.) was added, sealed, and heated at 70 ° C. for 30 minutes. To this, 1.0 mL of water and 1.5 mL of hexane were added and shaken. After standing, the upper layer was analyzed by gas chromatography (GLC), and the total amount of triterpene alcohol (% by mass) was measured. The same GLC analysis conditions as in (iii) were used.

(V) Samples were prepared according to γ-oryzanol Lipids, 30 (3), 269 (1995) and measured by HPLC-UV. Specifically, it measured by the following method.
About 100 mg of an oil and fat sample was dissolved in ethyl acetate to 10 mL, and analyzed by HPLC.
<HPLC analysis conditions>
Column: Inertsil ODS-3 4.6 mm × 250 mm, 5 μm (GL Science)
Column temperature: 40 ° C
Flow rate: 1.2 mL / min Detection: UV 325 nm
Eluent: acetonitrile / butanol / acetic acid (volume ratio 82/3/2)

(Vi) Fatty acid ester type triterpene alcohol The amount of free triterpene alcohol and the amount of γ-oryzanol converted to free type were subtracted from the total amount of triterpene alcohol to calculate the amount of fatty acid ester type triterpene alcohol converted to free type. Conversion from the free type to the fatty acid ester type was carried out to obtain the fatty acid ester type triterpene alcohol amount (% by mass). In addition, when converting from the free type to the fatty acid ester type, the calculation was performed assuming that the bound fatty acid was oleic acid.

[Free Triterpene Alcohol and Free Plant Sterol]
Free triterpene alcohol was prepared by hydrolyzing commercially available oryzanol (Wako Pure Chemical Industries, Ltd.), and separating and purifying by silica gel column chromatography. The composition of the preparation was 40% cycloartenol and 60% 24-methylenecycloartanol.
Free type plant sterol (4-desmethyl sterol) is prepared by hydrolyzing commercially available oryzanol (Wako Pure Chemical Industries, Ltd.), separated and purified by silica gel column chromatography, and commercially available plant sterol preparation ( ADM Co., Ltd.), β-sitosterol and campesterol (both manufactured by Tama Seikagaku Co., Ltd., purity 99%) were used. The composition of the preparation from oryzanol was 62% campesterol, 31% β-sitosterol and 6% stigmasterol. The composition of the plant sterol preparation (ADM Co., Ltd.) was campesterol 26%, β-sitosterol 51%, and stigmasterol 20%.

[Raw oil]
Table 1 shows the glyceride composition and fatty acid composition of the rapeseed white squeezed oil. Moreover, the free type and fatty acid ester type triterpene alcohol content and (gamma)-oryzanol content in rapeseed white squeezed oil were 0%.

[Preparation of oil and fat composition]
Examples 1-14 and Comparative Examples 1-9
For rapeseed white squeezed oil (manufactured by Nisshin Oillio Group Co., Ltd.), free triterpene alcohol, reagent β-sitosterol, reagent campesterol were blended in the proportions shown in Table 2, respectively, and the temperature was 50 ° The oil and fat composition was prepared by mixing and dissolving with a stirrer until the whole became clear while maintaining the temperature. The contents of free triterpene alcohol, free plant sterol, β-sitosterol and campesterol in each oil and fat composition are as shown in Table 2.

Examples 15-27 and Comparative Examples 10-17
For rapeseed white squeezed oil (manufactured by Nisshin Oillio Group Co., Ltd.), free triterpene alcohol and preparations from oryzanol (Examples 15 to 24 and Comparative Examples 10 to 17) at the ratios shown in Table 3. Commercially available plant sterol preparations (Examples 25 to 27) were blended, mixed and dissolved using a stirrer while maintaining a temperature of 50 ° C. until the whole was clarified, and oil and fat compositions were prepared. The contents of free triterpene alcohol, free plant sterol, β-sitosterol and campesterol in each oil and fat composition are as shown in Table 3.
In any of the oil and fat compositions, the fatty acid ester type triterpene alcohol content and the γ-oryzanol content were 0%.

20 g of the oil and fat composition prepared above was placed in a 30 mL vial and allowed to stand, and the storage stability was visually evaluated as follows.
[Evaluation of storage stability at 25 ° C.]
Nine panels evaluated the appearance when stored at 25 ° C. for 1 week according to the following evaluation criteria, and the average value was used as a storage stability score. The results are shown in Tables 2 and 3.
(Storage stability)
4: Good 3: Almost good but slightly hazy 2: Slightly inferior, slightly hazy 1: Inferior, cloudy

[Evaluation of cold resistance]
Nine panels evaluated the appearance when stored at 0 ° C. for 1 week according to the following evaluation criteria, and the average value was used as a storage stability score. The results are shown in Tables 2 and 3.
(Cold resistance)
4: Good 3: Almost good but slightly hazy 2: Slightly inferior, slightly hazy 1: Inferior, cloudy

[Evaluation of storage stability under high temperature humidification conditions]
Nine panels evaluated the appearance when stored at 80% humidity and 40 ° C. for 1 week according to the following evaluation criteria, and the average value was used as a storage stability score. The results are shown in Tables 2 and 3.
(Storage stability under high temperature humidification conditions)
4: Good 3: Almost good, but some crystals are deposited on the liquid surface 2: Slightly inferior, crystals are deposited on the liquid surface 1: Inferior, crystals are precipitated on the whole and become cloudy

  As shown in Tables 2 and 3, it was confirmed that the oil and fat composition of the present invention was superior in storage stability, particularly cold resistance and storage stability under high temperature humidification conditions, as compared with the comparative example.

Claims (8)

The following components (A) and (B):
(A) 0.4 to 6% by mass of a free-type tetracyclic triterpene alcohol having 30 or 31 carbon atoms,
(B) 0.2-2.5% by mass of a free 28- or 29-carbon 4-desmethylsterol containing 20% by mass or more of β-sitosterol,
Containing and free content mass ratio of the free-desmethyl sterols triterpene alcohol (B) [(A) / (B)] is fat composition is 0.9 or more (A).   The oil-and-fat composition according to claim 1, comprising 78-99.4% by mass of triacylglycerol.   The fat and oil composition according to claim 1 or 2, wherein the (B) free 28- or 29-carbon 4-desmethylsterol further contains campesterol.   The component (A) free tetracyclic triterpene alcohol having 30 or 31 carbon atoms is one or more selected from cycloartenol, 24-methylenecycloartanol and cyclobranol. Oil composition according to any one of the above.   Content of (gamma)-oryzanol is less than 0.7 mass%, The oil-fat composition of any one of Claims 1-4.   The fat composition according to claim 5, wherein the content of γ-oryzanol is less than 0.0034% by mass.   The fat and oil composition according to any one of claims 1 to 6, wherein the fatty acid ester type tetracyclic triterpene alcohol having 30 or 31 carbon atoms is less than 1.4% by mass.   The fat and oil composition according to claim 7, wherein the fatty acid ester type tetracyclic triterpene alcohol having 30 or 31 carbon atoms is less than 0.05% by mass.